KR100721600B1 - Biodegradable Grease Composition Using Distillation Residues Generated in Biodiesel Production - Google Patents

Abstract

A grease composition using lubricating base oil that is biodegradable by microorganisms in nature and has an affinity to the human body is provided. More particularly, a distillation residue secondarily generated in production of biodiesel from vegetable oil (soybean oil and canola oil) is used as the lubricating base oil. The grease composition is produced by adding 1 to 20wt% of additives to 100 to 95wt% of distillation residues, which is generated in production of biodiesel, and 1 to 30wt% of thickeners.

Description

Biodegradable Grease Composition Using Distillation Residue in Biodiesel Production {Composition of Grease prodnced from distillated Residuum}

The present invention relates to a grease for lubricating machinery, equipment and equipment used in the general industry, and more specifically, 10 to 95 weight of the final residue produced during biodiesel production using deodorized fatty acids of soybean oil and rapeseed oil. It is related with the grease composition manufactured using% base oil.

<Composition and Classification of General Greases>

Lubricant greases are classified into metal salt soap greases such as Ca, Na, Li, Al, Ba, and Complex, and soap-based greases such as Bentone, Silica, Urea, Graphite, and PTFE, depending on the type of thickener. Therefore, it is divided into mineral oil grease, synthetic oil grease and the like.

The grease function reduces friction between parts and parts of the lubrication area, reduces wear and wear, improves lubrication surface properties, reduces adhesion and melting of metal surfaces, and removes heat generated to remove heat deformation. It is to prevent the mixing of foreign matters generated during lubrication operation and to maximize the sealing effect, thus preserving the performance and life of the equipment and lubrication parts. As such grease base oils, petroleum hydrocarbon lubricating base oils produced in the last step of the crude oil refining process have been mainly used. However, grease using petroleum hydrocarbons as described above may cause environmental damage and may threaten the health of the person using such grease.

Recently, as the importance of environmental protection and the interest in health and safety for workers have increased all over the world, studies on water-soluble lubricating base oils to replace hydrocarbon-based lubricating base oils in Greece have already been carried out at the national level in North America and Western Europe. It's going on.

The present invention is to develop a grease composition using a distillation residue produced in the production of biodiesel from the lubricant base oil as an active ingredient of the grease composition in accordance with this trend.

Biodiesel is an alternative energy made by processing fat components in plants and animals to have properties similar to those of diesel, replacing diesel or mixing them with diesel. Biodiesel generally refers to fatty acid methyl ester made by reacting vegetable oil such as soybean oil or rapeseed oil with alcohol (usually methanol), and refers to a purity of 95% or more. (Ministry of Commerce, Industry and Energy Notice No. 2000-57)

The vegetable oil in the stomach is a compound containing a hydrophobic group that is insoluble in water, and is generally composed of triglycerides represented by the following chemical structural formula.

Vegetable fats and oils are generally characterized by the content of fatty acids. The length, content and saturation of the fatty acids that make up the fats and fats play an important role in determining the physical and chemical properties of the oil. Animal oils are less usable than plants, and only herds of land animals, pigs, cattle and sheep, and herring and menhaden sea animals are of commercial importance today. Animal oils, like vegetable oils, are composed of saturated and unsaturated triglycerides. Unlike vegetable oils, animal oils have a broad fatty acid distribution and contain some odd linear fatty acids.

Vegetable oil methyl ester and biodiesel are less toxic and biodegradable, so when they are spilled into the soil, soil contamination is less than that of hydrocarbon-based lubricants. It also contributes to national competitiveness by reducing 2.2 tonnes of CO2 when one tonne of vegetable oil methyl ester is used as a way of responding to the climate change agreement (Life Cycle CO2). Vegetable oil methyl ester is composed of Methyl Oleate and Methyl Linoleate as the main components, and has low viscosity (40, 1.9∼6.0 cSt). It has excellent lubricity and shows excellent performance in processability and detergency when used in place of petroleum hydrocarbon lubricant base oil.

CH3- (CH2) 14-COO-CH3: Methyl Palmitate

CH3- (CH2) 6-CH2-CH = CH-CH2- (CH2) 6-COO-CH3: Methyl Oleate

CH3- (CH2) 3-CH2-CH = CH-CH2-CH = CH-CH2- (CH2) 6-COO-CH3: Methyl Linoleate

Vegetable oil methyl ester is a methyl ester synthesized from vegetable oil and the manufacturing process is as follows.

Here, R, R 'and R "refer to saturated or unsaturated hydrocarbons with alkyl groups.

<Fatty acid composition of rapeseed oil and soybean oil to manufacture biodiesel>

<Chemical Structure of Fatty Acids Used in Greek Preparation>

<Biodegradability comparison of vegetable oil and synthetic ester base oil, CEC-L-33-A-93 method>

The compositional components and composition ratios of the vegetable oil methyl esters depend on the fatty acid component and composition ratio of the vegetable oil. The methyl esters of fatty acids shown in the following table are the components of vegetable oil methyl esters.

<Chemical structure of fatty acids that can be used for water-soluble metal covalent and used to prepare vegetable oil methyl esters>

Vegetable oils which can synthesize vegetable oil methyl esters that can be used in the present invention are shown in the following table.

<Fatty acid composition of vegetable oils that can produce biodiesel>

Biodiesel can be mixed with light oil or used as 100% biodiesel only. A mixture of 95% diesel and 5% biodiesel is called BD5 and 20% biodiesel is called BD20. Biodiesel has the effect of reducing the recycling of waste resources and CO2, which is a greenhouse gas, and because of the low emission of air pollutants, it is drawing attention as a future energy source at home and abroad. At present, the world is using biodiesel as a demonstration or increasing its supply through pilot projects. First of all, Europe is active in using alternative energy, and the biodiesel system is settled. It is formally recognized for use as long as it meets the specifications of general diesel. The European Diesel Standard (EN590), which entered into force in January 2004, recognizes up to 5% biodiesel as general diesel. In the United States, since the establishment of the National Biodiesel Board in 1992, the National Assembly and EPA have approved the BD20 as a diesel vehicle fuel since 1998. In 2001, President Bush began renewable energy, including biodiesel. We have expanded our spread. As the government announces the introduction actively, biodiesel's supply is increasing every year, and it is used in the army, air force, energy ministry, NASA, state vehicles and buses. In Korea, in May 2002, the Ministry of Commerce, Industry and Energy conducted a two-year pilot operation based on the notification of the Ministry of Commerce, Industry and Energy's promotion of biodiesel pilot projects. It is a situation. The biggest advantage of biodiesel is that it can reduce the smoke emitted from cars. While biodiesel does not emit CO2, a greenhouse gas, CO2 yields are very low throughout the life cycle of the process (from an overall point of view, from production to consumption), sulfur oxides (SOx) and particulate matter (PM). Somewhat less emissions. Since it is produced from plant resources, it can be produced in-house in Korea, which has advantages in terms of energy security. It also has the effect of reducing environmental pollution by utilizing waste resources such as waste cooking oil. In terms of infrastructure, diesel engines and gas station distribution networks can be used, which means that there is no additional cost. However, despite these advantages, there are various problems to replace the existing diesel or gasoline. In order to reduce harmful substances in automobile exhaust gas, the biodiesel compounding ratio should be increased. Biodiesel has a characteristic of corroding the engine, which may cause engine failure, and deteriorates when stored for a long time.

For this reason, vegetable oil methyl ester requires a higher purity product to be used as an automobile fuel oil, and thus undergoes a separate vacuum distillation process after the methyl ester reaction. Distillation under reduced pressure is carried out at 2 to 3 torr, about 240 max. After distillation under reduced pressure, the distillate is used as biodiesel fuel oil, and about 1 to 5% of distillation residue is additionally produced. Distillation residues produced during the production of biodiesel also have ester structure as reactants of vegetable oil, and can be used as eco-friendly lubricant base oil.

The present invention provides a grease composition comprising a distillation residue generated when biodiesel is produced using soybean oil and rapeseed oil as a base oil, and a combination of other thickeners and additives.

Thickeners include lithium soap-based, diurea-based, aluminum complex soap-based, bentonite-based, and additives such as pour point depressants, lubricating additives, structural stabilizers, antioxidants, and metal corrosion inhibitors. Only additives were used. Nitrite, Formaldehyde and its derivatives, which are additive ingredients that could be regulated in the future, were not used. Petroleum hydrocarbons are excluded.

The present invention relates to industrial lubricating grease, such as machinery and equipment, and more particularly, by mixing 10 to 95% by weight of distillation residues, 3 to 30% by weight of thickener and 3 to 50% by weight of additives A grease composition to be formulated.

In the present invention, the distillation residue of biodiesel is a distillation residue of biodiesel produced from soybean oil and rapeseed oil.

The thickener used in the present invention is classified into five kinds of lithium soap, aluminum soap, diurea (Di-Urea), benton (entone), and silica gel (Silica Gel) and at least one selected from these groups.

Lithium and aluminum soaps include soaps produced after saponification of lithium and aluminum metals with 12-Hydroxy Stearic Acid, Stearic Acid, Boric Acid, Benzoic Acid, H2O and the like.

The diurea thickener is composed of diisocyanate compounds such as tolylene diisocyanate compound, diphenylmethane diisocyanate, naphthalene, diisocyanate, monoamines such as benzylamine, toluidine, and coloaniline, tetradecylamine, pentadecylamine, Di-Urea reactants, which are reactants with groups such as hexadecylamine, heptadecylamine, octadecylamine, nonyldecylamine, eicosylamine, and the like.

Bentonic thickeners include alcohol or water as Bentonite and Self Activator.

Silica gel-based thickeners are Fumed Silica and include Hydorphobil (hydrophilic) and Hydrophilic (hydrophobic) Silica.

The additive used in the present invention includes a pour point lowering agent, a lubricating additive, a metal corrosion inhibitor, an antioxidant, a structural stabilizer, and a thickener. The additive used in the present invention is at least one selected from the group consisting of a flow point lowering agent, a lubricant additive, a metal corrosion inhibitor, an antioxidant, a structural stabilizer, and a thickener. Pour point depressants as additives used in the present invention include polymethacrylates, aromatic synthetic base oils and derivatives thereof. Lubricant additives include dithiocarbamate, arylphosphate-based, metal salts of phosphate esters, and sulfides and derivatives thereof. Anticorrosive agents include benzotriazole, tolytriazole, mercaptobenzothiazole and derivatives thereof. Antioxidants include tetrabutylmethylphenol, quinoline compounds and derivatives thereof. Structural stabilizers include copolymers such as ethylene propylene and derivatives thereof. Thickeners include derivatives such as polybutene and polyisobutylene.

EXAMPLE

The biodiesel distillation residue was used as base oil to prepare grease for each of the four thickeners, and then the physical properties and performance were measured.

Example 1 (lithium thickener)

Distillation residues produced during biodiesel production, lithium soaps (fatty acid and saponification reactions of lithium hydroxide and 12-Hydroxy Stearic Acid, Stearic Acid, Azelaic Acid, Boric Acid, etc.), Pour point enhancers, lubricant additives, metal corrosion inhibitors, antioxidants A lithium soap-based grease composition was prepared by adding a structural stabilizer and a thickener.

Table 1. Lithium soap-based grease composition and physical properties

Example 2 (Diurea type thickener)

Distillation residue produced when producing biodiesel, diurea thickener (Di-urea, tolylene diisocyanate compound, diisocyanate compound such as diphenylmethane diisocyanate, naphthalene diisocyanate, benzylamine, toluidine, coloaniline, etc.) Amine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonyldecylamine, aromatic amines such as eicosylamine), pour point depressant, lubricant additive, metal corrosion inhibitor, antioxidant, structural stabilizer Diurea grease composition was prepared by addition.

Table 2. Diurea Grease Composition and Properties

Example 3 (aluminum thickener)

Distillation residues produced during biodiesel production, aluminum complex thickeners (aluminum metal compounds and fatty acids Benzoic, Palmitic, Palmitoleic, Stearic, Oleic, Linoleic Acid), Pour point depressants, lubricant additives, metal corrosion inhibitors, antioxidants, structural stabilizers Was added to prepare an aluminum composite grease composition.

Table 3. Aluminum Grease Composition and Physical Properties

Example 4 (benton system thickener)

A Betone grease composition was prepared by adding distillation residue, Bentone thickener, pour point lowering agent, lubricating additive, metal corrosion inhibitor, antioxidant, and structural stabilizer.

Table 4. Bentone Grease Compositions and Properties

Example 5 (silica gel type thickener)

Silica grease was prepared by adding distillation residue, Silica Gel thickener, pour point depressant, lubricant additive, metal corrosion inhibitor, antioxidant, and structural stabilizer.

Table 5. Grease Composition and Physical Properties Using Silica Gel as Thickener

The present invention utilizes the distillation residue produced when producing biodiesel as an active ingredient of the grease composition as a base oil of grease, and has excellent lubricity compared to the use of conventional petroleum base oils. On the other hand, it is possible to supply eco-friendly grease of the same level at a low price and to obtain the effect of recycling the biodiesel distillate residue.

Claims (8)

A grease composition, which is prepared by combining 50 to 95% by weight of distillation residue, 3 to 30% by weight of thickener and 3 to 20% by weight of additives produced when producing biodiesel. The grease composition according to claim 1, wherein the distillation residue is a distillation residue produced when biodiesel is produced using soybean oil or rapeseed oil as a raw material, and the base oil kinematic viscosity (40, cSt) is in a range of 20 to 400. The grease composition according to claim 1, wherein the thickener is at least one selected from lithium soap based, diurea based, aluminum complex soap based, Bentone thickener or silica gel based. The grease composition according to claim 3, wherein the lithium soap-based thickener is at least one selected from lithium hydroxide metal compound and 12-Hydroxy Stearic, Stearic, Boric, Azelaic, Sebacic Acid. 4. The diurea-based compound according to claim 3, wherein the diurea-based compound is a diisocyanate compound, a monoamine such as benzylamine, toluidine, and coloaniline, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, and nonyl. A grease composition characterized by at least one selected from aromatic amines such as decylamine and eicosylamine. 4. The grease composition of claim 3, wherein the aluminum complex soap thickener is at least one selected from an aluminum metal compound and Benzoic, Stearic, Palmitic, Palmitoleic, and Oleic Acid. The grease composition according to claim 3, wherein the silica gel-based thickener is Fumed Silica and is used as a grease thickener by dispersing it in a base oil including hydrophobic and hydrophilic. The additive according to claim 1, wherein the additive is a lubricating agent including a polymethacrylate, an aromatic synthetic base oil and a derivative thereof and a lubricating agent including a dithiocarbamate, an aryl phosphate, a metal salt of a phosphate ester, a sulfide and a derivative thereof. And metal corrosion inhibitors including benzotriazole, tolytriazole, mercaptobenzothiazole and derivatives thereof, antioxidants including tetrabutylmethylphenol, quinoline compounds and derivatives thereof and copolymers such as ethylene propylene and the like A grease composition, characterized in that at least one of the structural stabilizers including derivatives